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BRITISH STANDARD BS EN

13130-2:2004

Materials and articles


in contact with
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foodstuffs Plastics
substances subject to
limitation
Part 2: Determination of terephthalic
acid in food simulants

The European Standard EN 13130-2:2004 has the status of a


British Standard

ICS 67.250

12&23<,1*:,7+287%6,3(50,66,21(;&(37$63(50,77('%<&23<5,*+7/$:
BS EN 13130-2:2004

National foreword

This British Standard is the official English language version of


EN 13130-2:2004. It supersedes DD ENV 13130-2:1999 which is withdrawn.
The UK participation in its preparation was entrusted by Technical Committee
CW/47, Materials and articles in contact with foodstuffs, to Subcommittee
CW/47/1, Migration from plastics, which has the responsibility to:
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aid enquirers to understand the text;


present to the responsible international/European committee any
enquiries on the interpretation, or proposals for change, and keep the
UK interests informed;
monitor related international and European developments and
promulgate them in the UK.

A list of organizations represented on this subcommittee can be obtained on


request to its secretary.
Cross-references
The British Standards which implement international or European
publications referred to in this document may be found in the BSI Catalogue
under the section entitled International Standards Correspondence Index, or
by using the Search facility of the BSI Electronic Catalogue or of British
Standards Online.
This publication does not purport to include all the necessary provisions of a
contract. Users are responsible for its correct application.
Compliance with a British Standard does not of itself confer immunity
from legal obligations.

This British Standard was Summary of pages


published under the authority
of the Standards Policy and This document comprises a front cover, an inside front cover, the EN title page,
Strategy Committee on pages 2 to 15 and a back cover.
16 June 2004
The BSI copyright notice displayed in this document indicates when the
document was last issued.

Amendments issued since publication

Amd. No. Date Comments


BSI 16 June 2004

ISBN 0 580 43932 1


EUROPEAN STANDARD EN 13130-2
NORME EUROPENNE
EUROPISCHE NORM May 2004

ICS 67.250
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English version

Materials and articles in contact with foodstuffs - Plastics


substances subject to limitation - Part 2: Determination of
terephthalic acid in food simulants

Matriaux et objets en contact avec les denres Werkstoffe und Gegenstnde in Kontakt mit Lebensmitteln
alimentaires - Substances dans les matires plastiques - Substanzen in Kunststoffen, die Beschrnkungen
soumises des limitations - Partie 2 : Dtermination de unterliegen - Teil 2: Bestimmung von Terephtalsure in
l'acide trphtalique dans les simulants d'aliments Prflebensmitteln

This European Standard was approved by CEN on 24 March 2004.

CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European
Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national
standards may be obtained on application to the Central Secretariat or to any CEN member.

This European Standard exists in three official versions (English, French, German). A version in any other language made by translation
under the responsibility of a CEN member into its own language and notified to the Central Secretariat has the same status as the official
versions.

CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France,
Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Slovakia,
Slovenia, Spain, Sweden, Switzerland and United Kingdom.

EUROPEAN COMMITTEE FOR STANDARDIZATION


COMIT EUROPEN DE NORMALISATION
EUROPISCHES KOMITEE FR NORMUNG

Management Centre: rue de Stassart, 36 B-1050 Brussels

2004 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 13130-2:2004: E
worldwide for CEN national Members.
EN 13130-2:2004 (E)

Contents
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Foreword..............................................................................................................................................................3
1 Scope ......................................................................................................................................................6
2 Normative references ............................................................................................................................6
3 Principle..................................................................................................................................................6
4 Reagents.................................................................................................................................................6
5 Apparatus ...............................................................................................................................................7
6 Samples ..................................................................................................................................................8
7 Procedure ...............................................................................................................................................8
7.1 Preparation of standards ......................................................................................................................8
7.2 Preparation of calibration graphs ........................................................................................................9
7.3 Validation of preparation of standard solutions.................................................................................9
7.4 Suitability of orthophthalic acid as an internal standard ..................................................................9
7.5 Extraction of olive oil simulant migration test samples ....................................................................9
7.6 Preparation of aqueous simulant migration samples......................................................................10
7.7 Injection of samples ............................................................................................................................10
8 Expression of results ..........................................................................................................................10
8.1 Method of calculation ..........................................................................................................................10
8.2 Precision...............................................................................................................................................10
9 Confirmation of terephthalic acid ......................................................................................................12
9.1 Requirement for confirmation ............................................................................................................12
9.2 Re-analysis using an ion exchange column .....................................................................................12
9.3 Multi-wavelength measurements/diode array spectra analysis .....................................................12
10 Test report ............................................................................................................................................13
Annex A (normative) Reagents for confirmation of terephthalic acid..........................................................14
A.1 Reagents for confirmation of terephthalic acid................................................................................14
Bibliography ......................................................................................................................................................15

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EN 13130-2:2004 (E)

Foreword
This document (EN 13130-2:2004) has been prepared by Technical Committee CEN/TC 194 Utensils in
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contact with food, the secretariat of which is held by BSI.

This document was prepared by Subcommittee SC1 of TC 194 as one of a series of analytical test methods
for plastics materials and articles in contact with foodstuffs.

This European Standard shall be given the status of a national standard, either by publication of an identical
text or by endorsement, at the latest by November 2004, and conflicting national standards shall be withdrawn
at the latest by November 2004.

This document has been prepared under a mandate given to CEN by the European Commission and the
European Free Trade Association.

This standard is intended to support Directives 2002/72/EC [1], 89/109/EEC [2], 82/711/EEC [3] and its
amendments 93/8/EEC [4] and 97/48/EC [5], and 85/572/EEC [6].

At the time of preparation and publication of this part of EN 13130 the European Union legislation relating to
plastics materials and articles intended to come into contact with foodstuffs is incomplete. Further Directives
and amendments to existing Directives are expected which could change the legislative requirements which
this standard supports. It is therefore strongly recommended that users of this standard refer to the latest
relevant published Directive(s) before commencement of a test or tests described in this standard.

EN 13130-2 should be read in conjunction with EN 13130-1.

Further parts of EN 13130, under the general title Materials and articles in contact with foodstuffs - Plastics
substances subject to limitation, have been prepared, and others are in preparation, concerned with the
determination of specific migration from plastics materials into foodstuffs and food simulants and the
determination of specific monomers and additives in plastics. The other parts of
EN 13130 are as follows.

Part 1: Guide to test methods for the specific migration of substances from plastics to foods and food
simulants and the determination of substances in plastics and the selection of conditions of exposure to food
simulants

Part 3: Determination of acrylonitrile in food and food simulants

Part 4: Determination of 1,3-butadiene in plastics

Part 5: Determination of vinylidene chloride in food simulants

Part 6: Determination of vinylidene chloride in plastics

Part 7: Determination of monoethylene glycol and diethylene glycol in food simulants

Part 8: Determination of isocyanates in plastics

Part 9: Determination of acetic acid, vinyl ester in food simulants

Part 10: Determination of acrylamide in food simulants

Part 11: Determination of 11-aminoundecanoic acid in food simulants

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EN 13130-2:2004 (E)

Part 12: Determination of 1,3-benzenedimethanamine in food simulants

Part 13: Determination of 2,2-bis(4-hydroxyphenyl)propane (Bisphenol A) in food simulants

Part 14: Determination of 3,3-bis(3-methyl-4-hydroxyphenyl)-2-indoline in food simulants

Part 15: Determination of 1,3-butadiene in food simulants


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Part 16: Determination of caprolactam and caprolactam salt in food simulants

Part 17: Determination of carbonyl chloride in plastics

Part 18: Determination of 1,2-dihydroxybenzene, 1,3- dihydroxybenzene, 1,4- dihydroxybenzene, 4,4-


dihydroxybenzophenone and 4,4dihydroxybiphenyl in food simulants

Part 19: Determination of dimethylaminoethanol in food simulants

Part 20: Determination of epichlorohydrin in plastics

Part 21: Determination of ethylenediamine and hexamethylenediamine in food simulants

Part 22: Determination of ethylene oxide and propylene oxide in plastics

Part 23: Determination of formaldehyde and hexamethylenetetramine in food simulants

Part 24: Determination of maleic acid and maleic anhydride in food simulants

Part 25: Determination of 4-methyl-pentene in food simulants

Part 26: Determination of 1-octene and tetrahydrofuran in food simulants

Part 27 Determination of 2,4,6-triamino-1,3,5-triazine in food simulants

Part 28: Determination of 1,1,1-trimethylopropane in food simulants

Parts 1 to 8 are European Standards.

Parts 9 to 28 are Technical Specifications, prepared within the Standards, Measurement and Testing project,
MAT1-CT92-0006, Development of Methods of Analysis for Monomers.

According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to implement this European Standard: Austria, Belgium, Cyprus, Czech Republic,
Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Slovakia, Slovenia, Spain, Sweden, Switzerland
and United Kingdom.

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EN 13130-2:2004 (E)

Introduction
Terephthalic acid (TA) is a comonomer used in the manufacture of polyester plastics. Residues of
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terephthalic acid can be present in the plastics after processing to form materials and articles intended to
come into contact with foodstuffs. When these plastics are in contact with foodstuffs, the residual terephthalic
acid monomer can migrate into the foodstuff.

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EN 13130-2:2004 (E)

1 Scope
This part of this European Standard specifies methods for the determination of the monomer terephthalic acid
in food simulants; distilled water, 3 % (w/v) acetic acid aqueous solution, 15 % (v/v) ethanol aqueous solution
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and olive oil and other fatty food simulants, simulants D, e.g. a mixture of synthetic triglycerides or sunflower
oil or corn oil. The methods are capable of determining terephthalic acid in the food simulants at the level of
the specific migration limit of 7,5 mg of terephthalic acid per kilogram of food simulants.

NOTE This method was developed for the determination of terephthalic acid in 15 % (v/v) aqueous ethanol, as
required by the regulations in force at the time the development work was carried out. However, this method, developed
for 15 (v/v) aqueous ethanol, should be applicable to the determination in 10 (v/v) aqueous ethanol.

2 Normative references
This European Standard incorporates by dated or undated reference, provisions from other publications.
These normative references are cited at the appropriate places in the text, and the publications are listed
hereafter. For dated references, subsequent amendments to or revisions of any of these publications apply to
this European Standard only when incorporated in it by amendment or revision. For undated references the
latest edition of the publication referred to applies (including amendments).

EN 13130-1:2004; Materials and articles in contact with foodstuffs - Plastics substances subject to limitation -
Part 1: Guide to test methods for the specific migration of substances from plastics to foods and food
simulants and the determination of substances in plastics and the selection of conditions of exposure to food
simulants

EN ISO 1042; Laboratory glassware One-mark volumetric flasks (ISO 1042:1998).

ISO 385 (all parts); Laboratory glassware Burettes.

ISO 648; Laboratory glassware One-mark pipettes.

ISO 835 (all parts); Laboratory glassware Graduated pipettes.

ISO 4788, Laboratory glassware Graduated measuring cylinders.

3 Principle
The aqueous simulant test samples are directly analysed by high performance liquid chromatography (HPLC)
with ultraviolet (UV) detection. The olive oil test samples are extracted with dilute sodium hydrogen carbonate
and the resultant aqueous solution is acidified and analysed by HPLC.

4 Reagents
WARNING: All chemicals are hazardous to health to a greater or lesser extent. It is beyond the scope
of this standard to give instructions for the safe handling of all chemicals, that meet, in full, the legal
obligations in all countries in which this standard can be followed. Therefore, specific warnings are
not given and users of this standard shall ensure that they meet all the necessary safety requirements
in their own country.

NOTE During the analysis, unless otherwise stated, only reagents of recognized analytical grade and only distilled
water of equivalent purity should be used.

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EN 13130-2:2004 (E)

4.1 Methanol (HPLC grade).

4.2 Sodium acetate, trihydrate.

4.3 Orthophthalic acid.

4.4 Terephthalic acid.


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4.5 Orthophosphoric acid 85 % (w/v).

4.6 Water (HPLC grade).

4.7 Sodium hydrogen carbonate solution 0,1 % (w/v).

4.8 Acetic acid, 50 % (v/v) in water.

4.9 Propan-2-ol.

4.10 Heptane.

4.11 pH 3,6 buffer solution.

Dissolve 25,0 g of sodium acetate, trihydrate in 350 ml of water, add 5,0 ml 0,1 ml of orthophosphoric acid
and adjust to pH (3,6 0,2) with glacial acetic acid (approximately 50 ml). Make up to 500 ml with water.

4.12 Weigh accurately about 0,05 g terephthalic acid and, by continuous stirring, dissolve in about 90 ml
of methanol. Make up to 100 ml with methanol in a volumetric flask. Prepare a second terephthalic acid
standard stock solution for validation purposes, see 7.3.

NOTE The solution can be warmed to 50 C to facilitate dissolution of the terephthalic acid, which takes at least 1 h.

4.13 Orthophthalic acid internal standard stock solution.

Weigh about 0,1 g of orthophthalic acid and dissolve in propan-2-ol. Make up to 100 ml with propan-2-ol in a
volumetric flask.

4.14 Mobile phase for high performance liquid chromatography.

Using a measuring cylinder add 150 ml of methanol to 150 ml of pH 3,6 buffer and dilute to 1 l with water.

NOTE Degassing the mobile phase can be necessary with some HPLC equipment.

5 Apparatus
5.1 Analytical balance capable of weighing accurately to 0,1 mg.

5.2 pH meter with an accuracy of pH 0,1.

5.3 Volumetric flasks, of 25 ml, 50 ml and 100 ml capacity, conforming to the minimum requirements of EN
ISO 1042.

5.4 Measuring cylinders, of 5 ml, 25 ml, 50 ml, 100 ml and 250 ml capacity, conforming to the minimum
requirements of ISO 4788.

5.5 Pipettes, of 5 ml and 50 ml capacity, conforming to the minimum requirements of ISO 648.

5.6 Graduated pipette, of 2 ml capacity, conforming to the minimum requirements of ISO 835.

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EN 13130-2:2004 (E)

5.7 Separating funnels, of 250 ml capacity.

5.8 Glass syringe, of 50 ml capacity.

5.9 Octadecylsilyl silica (ODS) 400 mg, C18 reverse phase disposable cartridges.

5.10 HPLC 0,2 m membrane filters.


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5.11 Burette, of 25 ml capacity, conforming to the minimum requirements of ISO 385.

5.12 High performance liquid chromatograph with a 10 l injection loop, and a variable wavelength UV
detector, set to 242 nm, connected to a strip chart recorder or integrator.

The column shall be capable of fully resolving terephthalic acid from orthophthalic acid, isophthalic acid and
peaks arising from injection media.

NOTE The following column has been found to be suitable: ODS 5 m 250 mm x 4,6 mm column, with a pre-column.
With a flow rate of 1,5 ml/min, orthophthalic acid and terephthalic acid have retention times of 4,7 min and 6,9 min
respectively.

With other reverse phase columns, adjustments can be made to the methanol concentration of the mobile
phase to give acceptable retention times.

6 Samples
The food simulant samples for testing shall have been prepared as described in EN 13130-1. Blank samples
of the food simulants are also required. For each simulant, 50 ml samples are required for each test.

7 Procedure

7.1 Preparation of standards

7.1.1 Intermediate standards

Prepare freshly on the day of use. Into five 25 ml volumetric flasks add, by burette, 1,0 ml, 2,0 ml, 5,0 ml, 10,0
ml, and 20,0 ml of the terephthalic acid stock solution (4.12). Into each add, by pipette, 5 ml of the
orthophthalic acid internal standard stock solution (4.13) and dilute to the mark with methanol. These
standards contain 20 mg/l, 40 mg/l, 100 mg/l, 200 mg/l, and 400 mg/l terephthalic acid.

7.1.2 Internal standard

Pipette 5 ml of the orthophthalic acid internal standard stock solution (4.13) into a 25 ml volumetric flask and
dilute to the mark with methanol.

7.1.3 Working standards for aqueous simulants

Pipette 2 ml of each intermediate standard into five 100 ml conical flasks, and add, by pipette, 50 ml of water
to give working standards containing approximately 0,8 mg/l, 1,6 mg/l, 4,0 mg/l, 8,0 mg/l and 16,0 mg/l
terephthalic acid. Pipette 2 ml of the internal standard (7.1.2) into a further 100 ml conical flask and add, by
pipette, 50 ml of water to give a blank standard 0,0 mg/l terephthalic acid.

7.1.4 Working standards for olive oil simulant

Weigh 50 g 1 g of the olive oil blank from the migration test into a 250 ml separating funnel. Add, by pipette,

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EN 13130-2:2004 (E)

2 ml of the first intermediate standard, mix well and add 50 ml 2 ml of heptane rinsing the measuring
cylinder in the process. Mix, and add 20 ml 1 ml of dilute sodium hydrogen carbonate solution using a
measuring cylinder.

Shake gently for 1 min, then allow 15 min for the phases to separate.

NOTE This is facilitated by holding the separating funnel at an angle of about 45 and slowly rotating it.
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Run off the lower aqueous layer into a 100 ml beaker and re-extract the oil with a further 20 ml 1 ml of
sodium hydrogen carbonate solution. Allow the phases to separate and run off the lower aqueous layer into
the beaker to combine the extracts. Pass the aqueous solution through a C18 cartridge using a syringe or
suction with a flow rate of about 10 ml/min to 20 ml/min. Collect the eluent into a 50 ml volumetric flask, add 1
ml 0,1 ml of 50 % acetic acid using a graduated pipette and dilute to the mark with water, mixing thoroughly.
Filter 1 ml to 2 ml through a 0,2 m filter for subsequent analysis in 7.2. Repeat this procedure for each
intermediate standard, and the internal standard (7.1.2), to give working standards containing 0 mg/kg, 0,8
mg/kg, 1,6mg/kg, 4,0 mg/kg, 8,0 mg/kg, and 16,0 mg terephthalic acid per kilogram of olive oil

7.2 Preparation of calibration graphs

Inject the two sets of working standards into the high performance liquid chromatograph using a 10 l loop.
Divide the terephthalic acid peak height or area by the orthophthalic acid peak height or area and plot these
values against the concentration of terephthalic acid in the standards in milligrams per litre, for both the
aqueous and the olive oil simulant.

The calibration graphs shall have a correlation coefficient of better than 0,997.

7.3 Validation of preparation of standard solutions

Dilute 10 ml of the second stock terephthalic acid standard solution (4.12) and 5 ml of the orthophthalic acid
internal standard stock solution (4.13) to 25 ml as described in 7.1.1 to obtain a 200 mg/l intermediate
standard. Dilute the intermediate standard as described in 7.1.3 to prepare a second 8,0 mg/l working
standard and inject in duplicate for HPLC analysis.

Calculate the terephthalic acid/orthophthalic acid peak ratio and the mean concentration of terephthalic acid
found in the second working standard by interpolation using the calibration graph obtained in 7.2, correcting
for the mass of terephthalic acid used to prepare the first stock solution. The mean concentration shall be
within 0,5 mg/l of the actual terephthalic acid concentration in the second working standard, calculated from
the mass of terephthalic acid used to prepare the second stock standard and the dilution factor. If the
concentration is not within 0,5 mg/l, reject all solutions and start again.

7.4 Suitability of orthophthalic acid as an internal standard

Carry out the instructions described in 7.5 and 7.6, for each simulant, but omitting addition of the internal
standard in each case. Inject each sample and the blank simulant prepared in this fashion and measure the
peak area of any peak with a retention time equal to that of orthophthalic acid, measured from the standard
chromatograms. After correction for the blank, if the interfering peak area exceeds 5 % of the orthophthalic
acid peak area measured from injection of the standards, seek an alternative internal standard.

NOTE Isophthalic acid has been found to be a suitable alternative, and has a longer retention time than terephthalic
acid.

7.5 Extraction of olive oil simulant migration test samples

Weigh 50 g 1g of the olive oil samples directly from the migration cell or container into a 250 ml separating
funnel. Add, by pipette, 2 ml of the internal standard solution (7.1.2), and mix thoroughly. Rinse the
measuring cylinder with 50 ml 2 ml of heptane and transfer to the separating funnel.

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EN 13130-2:2004 (E)

Extract twice with dilute sodium hydrogen carbonate and continuing the procedure described in 7.1.4 to
prepare the sample for analysis in 7.7.

7.6 Preparation of aqueous simulant migration samples

Pipette 2 ml of the internal standard solution (7.1.2) into a series of 100 ml conical flasks and add, by pipette,
50 ml of each sample, mixing thoroughly. Prepare blanks for each aqueous simulant in a similar fashion.
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7.7 Injection of samples

If the aqueous food simulant samples contain suspended solids, filter using a 0,2 m disposable HPLC
membrane filter. Inject the samples prepared in 7.5 and 7.6 into the HPLC using the 10 l loop, together with
the blanks prepared in 7.6. Divide the terephthalic acid peak height or area by the orthophthalic acid peak
height or area, correct for the blank, if necessary, and read from the appropriate graph the concentration of
terephthalic acid in milligrams per litre. Correct this value for the actual mass of terephthalic acid used to
prepare the stock solution (4.12).

8 Expression of results

8.1 Method of calculation

8.1.1 As milligrams of terephthalic acid per kilogram of food simulant

The procedure yields the concentration in milligrams per litre for aqueous food simulants and milligrams per
kilogram for olive oil and simulants D.

NOTE Commission Directive 2002/72/EC [1] states that the specific gravity of all simulants should conventionally be
assumed to be 1. Milligrams of substance released per litre of simulant thus corresponds numerically to milligrams of
substance released per kilogram of simulant and, taking into account of the provisions laid down in Directive 82/711/EEC,
to milligrams of substance released per kilogram of foodstuff.

The migration results obtained above as milligrams per litre equate numerically as milligrams per kilogram.

8.1.2 As milligrams of terephthalic acid per square decimetre of surface area of plastics material or
article

From the total volume or mass of simulant and surface area of plastics employed in the migration test,
calculate the migrated quantity of terephthalic acid in milligrams per square decimetre.

8.1.3 Calculation of the specific migration

Depending on the fill volume of the test material and on the surface area/food simulant ratio, the terephthalic
acid concentration in the laboratory sample as determined according to clause 7 can need mathematical
transformation in order to calculate the specific migration value to be compared with SML. For guidance see
EN 13130-1:2004, clause 13.

8.2 Precision

8.2.1 General

Method performance has been evaluated by carrying out a precision experiment according to ISO 5725-
1:1994 and ISO 5725-2:1994.

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EN 13130-2:2004 (E)

8.2.2 For validation of this method a precision experiment was conducted in 1997, involving twelve
laboratories. Each participant in this experiment obtained six samples of 10 % (v/v) aqueous ethanol fortified
with terephthalic acid at levels as follows in Table 1.

Table 1 Levels of terephthalic acid in 10 % (v/v) aqueous ethanol

solution level of terephthalic acid


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mg/kg
TAC1 solution level I 5,32
TAC2 solution level I 5,32
TAC3 solution level II 7,2
TAC4 solution level II 7,2
TAC5 solution level III 10,56
TAC6 solution level III 10,56

For validation of this method a precision experiment was conducted in 1997, involving eleven laboratories.
Each participant in this experiment obtained six samples of olive oil fortified with terephthalic acid at levels as
follows in Table 2.

Table 2 Levels of terephthalic acid in olive oil

solution level of terephthalic acid


mg/kg
TAD1 solution level I 7,31
TAD2 solution level I 7,31
TAD3 solution level II 11,00
TAD4 solution level II 11,00
TAD5 solution level III 5,37
TAD6 solution level III 5,37

Calibration solutions were prepared with comparable concentrations so that the calibration samples could be
corrected.

8.2.3 Repeatability and reproducibility

Evaluation of the results of the precision experiment for terephthalic acid for the 95% probability level yielded
the following performance characteristics in Table 3:

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EN 13130-2:2004 (E)

Table 3 Repeatability and reproducibility for the determination of terephthalic acid

range r R
5,3 mg/kg to 10,6 mg/kg in 10 % (v/v) aqueous ethanol 0,324 1,147
5,4 mg/kg to 11 mg/kg in olive oil 0,639 3,064
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The difference between two single results found on identical test material by one operator using the same
apparatus within the shortest feasible time interval is expected to exceed the repeatability value, r, on average
not more than once in 20 cases in the normal and correct operation of the method.

Single results on identical test material reported by two laboratories is expected to differ by more than the
reproducibility value, R, on average not more than once in 20 cases in the normal operation of the method.

8.2.4 Detection limit

The detection limit (DL) based on a signal to noise ratio of 3 was found to be in the region of 0,2 mg/l,
although detector and pump design, injection loop size, etc. could influence this value significantly.

9 Confirmation of terephthalic acid

9.1 Requirement for confirmation

In cases where terephthalic acid migration from materials and articles into foods, or food simulants, as
determined according to 8.1, exceeds a restriction criterion, e.g. SML = 7,5 mg/kg, the determination shall be
confirmed by one of either of the methods described in 9.2 or 9.3.

9.2 Re-analysis using an ion exchange column

The samples and standards can be reinjected for analysis using a high performance liquid chromatograph
fitted with an ion exchange column (10 m, polystyrene divinylbenzene, trimethyl ammonium exchanger). The
mobile phase suitable for this type of column is 0,2 mol/l ammonium chloride with the pH adjusted with 5 %
disodium tetraborate aqueous solution. With a flow rate of 2 ml/min, the retention time for terephthalic acid is
4,4 min and orthophthalic acid 9,0 min. See annex A for a list of the reagents.

The ammonium chloride concentration can be adjusted to obtain satisfactory retention times, if necessary.

To obtain reproducible results for the acetic acid simulant samples (as prepared in 7.6) the acidity shall be
neutralized to pH 7 to pH 8, before injection, by addition of 2 mol/l sodium hydroxide drop by drop, while
monitoring the pH using a pH meter. The standards and samples are injected as described in 7.2 and 7.7,
and the results calculated. The results from the two columns shall agree to within 10 % for a tentative
confirmation.

For both columns the peaks due to terephthalic acid shall maximize within 2 % of the absolute retention time.

9.3 Multi-wavelength measurements/diode array spectra analysis

Obtain further confirmatory evidence by comparing the relative responses at different wavelengths using the
ion exchange separation as follows. Set the wavelength on the variable wavelength UV detector to 242 nm
and inject the samples and a standard of similar terephthalic acid concentration. Reset the wavelength to 220
nm and 254 nm and repeat the injections. If adjustable, set the bandpass on the detector on its minimum
value.

12
EN 13130-2:2004 (E)

Calculate the ratios of the peak areas at the three wavelengths for the samples and the standard(s).

NOTE This procedure can be facilitated using a diode array detector to provide a UV spectrum for samples and the
standard(s).

Satisfactory confirmatory evidence is obtained if the peak area ratios are within 5 %, and the requirements in
9.1 are met.
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10 Test report

The test report shall contain the following, where known:

a) a reference to this part of this standard;


b) all information necessary for complete identification of the sample;
c) form of the plastics;
d) use /class of food for which the sample is intended to contact, where known, and where possible food
classification reference number as listed in Table 2 of EN 13130-1:2004;
e) intended conditions of use, where known;
f) conditions of the test;
1) foodstuffs or food simulants used;
2) duration and temperature, and relation with "Conditions of contact in worst foreseeable use", as
defined in Table 3 of EN 13130-1:2004;
3) area and geometry of the test specimen;
4) volume of foodstuff or food simulant used where appropriate;
g) any departures from the standard method, reasons for the departures;
h) any particular requirements of the parts of this standard;
i) any relevant comments on the test results;
j) details of any confirmation procedure(s);
k) limitation on the substance, that is a specific migration limit of 7,5 mg of terephthalic acid/kilogram of
food or food simulant;
l) identity of the laboratory conducting the test and the name of the analyst;
m) date of sample arrival or sampling, the method of sampling, the date of the analysis, together with note
on any intervening storage conditions;
n) individual test results, and the mean of two or more determinations satisfying the repeatability criterion
of 8.2.3, expressed in milligrams of terephthalic acid per kilogram of food simulant.

13
EN 13130-2:2004 (E)

Annex A
(normative)

Reagents for confirmation of terephthalic acid


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A.1 Reagents for confirmation of terephthalic acid


A.1.1 Ammonium chloride

A.1.2 Disodium tetraborate

A.1.3 Sodium hydroxide 2 mol/l

A.1.4 Mobile phase for ion chromatography

Dissolve 10,7 g of ammonium chloride in 500 ml of water and adjust the pH to 7,8 to 8,0 using the 5 % sodium
tetraborate solution. Dilute to 1 l with water.

14
EN 13130-2:2004 (E)

Bibliography

ISO 5725-1:1994, Accuracy (trueness and precision) of measurement methods and results Part 1: General
principles and definitions
Licensed Copy: AUB User, na, Fri Oct 19 19:44:55 GMT+00:00 2007, Uncontrolled Copy, (c) BSI

ISO 5725-2:1994, Accuracy (trueness and precision) of measurement methods and results Part 2: Basic
methods for the determination of repeatability and reproducibility of a standard measurement method

[1] Commission of the European Communities, Commission Directive 2002/72/EC of 6 August 2002 relating to
plastics materials and articles intended to come into contact with foodstuffs, Official Journal of the European
Communities, 15 August 2002, no. L 220, p18.

[2] Commission of the European Communities, Council Directive of 21 December 1988 on the approximation
of the laws of the Member States relating to materials and articles intended to come into contact with foodstuff
(89/109/EEC), Official Journal of the European Communities, 11 February 1989, no. L 40, p 38.

[3] Commission of the European Communities, Council Directive of 18 October 1982 laying down the basic
rules necessary for testing migration of the constituents of plastics materials and articles intended to come into
contact with foodstuffs (82/711/EEC), Official Journal of the European Communities, 23 October 1982, no. L
297, p 26.

[4] Commission of the European Communities, Commission Directive of 15 March 1993 amending Council
Directive 82/711/EEC laying down the basic rules necessary for testing migration of the constituents of
plastics materials and articles intended to come into contact with foodstuffs (93/8/EEC), Official Journal of the
European Communities, 14 April 1993, no. L 90, p 22.

[5] Commission of the European Communities, Commission Directive of 97/48/EC of 29 July 1997 amending
Council Directive 82/711/EEC laying down the basic rules necessary for testing migration of the constituents
of plastics materials and articles intended to come into contact with foodstuffs, Official Journal of the European
Communities, 12 August 1997, no. L 222, p 10.

[6] Commission of the European Communities, Council Directive of 19 December 1985 laying down the list of
simulants to be used for testing migration of constituents of plastics materials and articles intended to come
into contact with foodstuffs (85/572/EEC), Official Journal of the European Communities, 31 December 1985,
no. L372, p14.

15
BS EN
13130-2:2004
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